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EP0767728B2 - Verfahren und vorrichtung zur schaumherstellung mittels unter druck gelöstem kohlendioxid - Google Patents

Verfahren und vorrichtung zur schaumherstellung mittels unter druck gelöstem kohlendioxid Download PDF

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Publication number
EP0767728B2
EP0767728B2 EP95924245A EP95924245A EP0767728B2 EP 0767728 B2 EP0767728 B2 EP 0767728B2 EP 95924245 A EP95924245 A EP 95924245A EP 95924245 A EP95924245 A EP 95924245A EP 0767728 B2 EP0767728 B2 EP 0767728B2
Authority
EP
European Patent Office
Prior art keywords
carbon dioxide
screens
foam
mixture
reactive
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP95924245A
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English (en)
French (fr)
Other versions
EP0767728B1 (de
EP0767728A1 (de
Inventor
Robert Eiben
Wilfried Ebeling
Hans-Michael Sulzbach
Reiner Raffel
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer AG
Hennecke GmbH
Original Assignee
Bayer AG
Hennecke GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
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Application filed by Bayer AG, Hennecke GmbH filed Critical Bayer AG
Publication of EP0767728A1 publication Critical patent/EP0767728A1/de
Application granted granted Critical
Publication of EP0767728B1 publication Critical patent/EP0767728B1/de
Publication of EP0767728B2 publication Critical patent/EP0767728B2/de
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B29C44/34—Auxiliary operations
    • B29C44/36—Feeding the material to be shaped
    • B29C44/46—Feeding the material to be shaped into an open space or onto moving surfaces, i.e. to make articles of indefinite length
    • B29C44/461—Feeding the material to be shaped into an open space or onto moving surfaces, i.e. to make articles of indefinite length dispensing apparatus, e.g. dispensing foaming resin over the whole width of the moving surface
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B29C44/34—Auxiliary operations
    • B29C44/3469—Cell or pore nucleation
    • B29C44/3473—Cell or pore nucleation by shearing forces
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B29C44/34—Auxiliary operations
    • B29C44/3469—Cell or pore nucleation
    • B29C44/348—Cell or pore nucleation by regulating the temperature and/or the pressure, e.g. suppression of foaming until the pressure is rapidly decreased
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S261/00—Gas and liquid contact apparatus
    • Y10S261/26—Foam

Definitions

  • the present invention relates to a method and a device according to the preambles of claims 1 and 4, respectively.
  • a method and such a device are known e.g. from US-A-3 184 419.
  • the expandable substances used are in particular liquid starting products for plastics, which cure to form foamed plastics due to a polyaddition reaction or polycondensation reaction which commences after the expansion.
  • the invention relates specifically to polyurethane foams.
  • a liquid or gaseous expanding agent is added to at least one of the reactive components (polyisocyanate and compounds containing hydrogen atoms reactive with isocyanate groups, in particular polyols).
  • the other component is then added with mixing and the mixture obtained is conveyed either batchwise into a mold or continuously on a conveyor belt, where the mixture foams and cures.
  • Liquids such as low-molecular chlorofluoro-carbons, methylene chloride, pentane and the like
  • These materials evaporate out of the liquid reaction mixture and form bubbles. It is also possible to force air into the reaction mixture or into one of the components (mechanical foam production).
  • Liquid carbon dioxide has already often been proposed as an expanding agent on the grounds of environmental acceptability and industrial hygiene arid owing to the comparatively high solubility of liquid carbon dioxide in the polyol component See, for example British patent 803,771 and U.S. patents 3,181,199, 3,184,419, 4,337,318 and 5,120,770.
  • liquid carbon dioxide has not gained acceptance in practice, apparently due to the difficulties of producing uniform foams during the necessary expansion of the reaction mixture from pressures of between 10 and 20 bar.
  • the problem is, on one hand, that the carbon dioxide vaporizes relatively suddenly so that a very large increase in volume takes place in the reaction mixture, for example, by a factor of approximately 10, which is difficult to control.
  • reaction mixture tends to inhibit release of the carbon dioxide, which can be from 3 to 6 bar below the equilibrium vapor pressure of CO 2 at the relevant temperature, so that a sudden explosive release of carbon dioxide occurs, with the result that large voids or bubbles are enclosed within the foam.
  • US 3,108,976 discloses an apparatus in which an organic liquid and carbon dioxide are passed through a frothing zone consisting of fine meshed screens or perforated plates.
  • the present invention provides a device for the delivery of a foamable, two-component reactive mixture, which contains liquid carbon dioxide, from a mixing device where the reactive components are mixed into a mold or onto a conveyor belt, characterized in that at least two fine-meshed screens in tantem are located between the mold or conveyor belt and the mixing device, and wherein the screens in tandem are not more than 5 mm apart.
  • the present invention also provides a process for the production of foams from at least two reactive components using carbon dioxide as expanding agent, comprising mixing at least one of the reactive components with carbon dioxide under pressure thereby producing a mixture containing liquid carbon dioxide, mixing the resultant mixture with the other reactive component to form a foamable reactive mixture at a pressure in excess of the equilibrium pressure of dissolved carbon dioxide, expanding the reactive mixture and curing the resultant foam product, characterized in that the foamable reactive mixture is expanded by passing said reactive mixture through at least one fine-meshed screen with subdivision into a large number of individual flows at shear rates of above 500/sec.
  • the present invention is in the field of production of foams from multicomponent plastics, in particular two-component plastics, using carbon dioxide as expanding agent, by mixing at least one of the reactive components with carbon dioxide under pressure, mixing the component containing the carbon dioxide with another reactive component or the second reactive component under pressure, expanding the mixture and curing. This expansion is achieved by expanding the mixture of reactive components containing the carbon dioxide at ambient pressure through the device of the invention.
  • mixture containing liquid carbon dioxide means a homogeneous liquid under a pressure of at least 4 bar, wherefrom carbon dioxide is released after expansion to a pressure of less than at least 4 bar.
  • the mixture containing liquid carbon dioxide can be prepared by dissolving gaseous or solid carbon dioxide in at least one reactive component or by mixture with liquid carbon dioxide.
  • Suitable fine-meshed screens are of steel or textile fabric which is resistant to the reaction mixture, which have mesh sizes of from 0.025 to 0.3 mm, preferably from 0.05 to 0.2 mm, and most preferably from 0.05 to 0.15 mm.
  • the viscosity of the reaction mixture containing liquid carbon dioxide can be from 200 to 2,000 mPa.s, preferably from 300 to 800 mPa.s. Taking the viscosity into consideration, the shear stress of the mixture during the passage through the screen is preferably from 200 to 1,000 Pa.
  • the required pressure of the reaction mixture prior to the passage through the screens is dependent on the quantity of liquid carbon dioxide dissolved.
  • the equilibrium pressure is 7 bar at a carbon dioxide content of 2% by weight in the reaction mixture, and 11 bar at a carbon dioxide content of 4% by weight in the reaction mixture (the temperature of the reaction mixture is the same as the ambient temperature).
  • the pressure of the reaction mixture prior to the passage through the screens is preferably 1.1 times to 1.8 times, particularly preferably 1.3 times to 1.6 times, the equilibrium pressure.
  • the equilibrium pressure is the pressure where a carbon dioxide atmosphere present above the reaction mixture is in equilibrium with the dissolved carbon dioxide.
  • a pressure in excess of the equilibrium pressure is necessary prior to the passage through the screen, so that the mixture is still homogeneous on entering the screen, that is, that there is still no formation of gas bubbles prior to the passage through the screen.
  • the pressure can be throttled from above equilibrium pressure to a pressure below the equilibrium pressure. Throttling can be by means of a perforated or slotted plate arranged at a distance of 0.5 to 3 mm from the screens, with the width of the orifices being from 3 to 15 mm and the free surface of the passage being from 1 to 10% of the surface of the perforated plate.
  • the pressure of the mixture prior to entering the screens is preferably from 0.5 to 0.8 of the equilibrium pressure.
  • a liquid polyurethane foam having a density of from 50 to 80 kg/m 3 is successfully produced with a charge of from 2 to 3% by weight of CO 2 based upon the weight of the reaction mixture.
  • an expanding agent water which also produces carbon dioxide as an expanding gas in a reaction with isocyanate.
  • the screens are not more than 5 mm apart, particularly preferably from 0.5 to 3 mm apart
  • Figure 1 illustrates the principle according to the invention of producing high shear during the passage through the screen.
  • the enlarged cross-section through filaments 1a to 1d of the screen running perpendicular to the plane of the drawing is shown.
  • the velocity profiles 2, 3 and 4 of the reaction mixture are shown at the distances A, B and C from the mid-plane of the screen.
  • FIG. 2 shows schematically in general form the method for producing polyurethane foam.
  • Polyol is pumped from a storage tank 1 via a metering pump 2 into the static mixer 3.
  • Liquid carbon dioxide is also fed from the tank 4 via the heat exchanger 5 to the static mixer and here mixed with the polyol.
  • the mixing in the static mixer 3 is carried out preferably at a pressure P of from 60 to 150 bar, measured at the outlet of the static mixer.
  • the use of the heat exchanger 5 ensures that the reaction mixture remains below the critical temperature of 31°C, even after possible heat uptake from pumps and mixing units.
  • the mixture of polyol and liquid carbon dioxide is fed to the mixing head 6, where mixing with the isocyanate (arrow 7) and other additives such as foam stabilizers (arrow 8) takes place.
  • the expanding device 10 according to the invention is flange-mounted at the outlet 9 of the mixing head 6.
  • FIG. 3 shows an embodiment of the expanding device 10 according to the invention.
  • the expanding device consists of a tube 18, which can optionally have an enlargement and wherein screens 21a, 21b and 21c can be fastened at the ends by the threaded joint 19.
  • the screens are pressed against one another by means of distance plates 22a to 22d made of a soft metal such as aluminum or copper.
  • the reaction mixture containing liquid carbon dioxide encounters the screens in the direction of the arrow 23 and leaves as a liquid foam along arrows 24.
  • Figure 3a shows an embodiment of the expanding device according to the invention as in Figure 3, wherein a baffle 60 having several orifices 61 is arranged at a small distance in front of the screen.
  • the orifices define a free cross-sectional area equal to 4% of the perforated plate.
  • Figure 4 shows an arrangement for the production of block foam using the expansion device according to the invention.
  • the reaction mixture passes through the expansion device 10, leaves as liquid foam 30 and is deposited on the lower lining sheet 31, which runs on a conveyor belt (not shown).
  • the upper lining sheet 32 is guided over a roller 33 which dips into the foam which is deposited on the lower lining sheet 31 and thereby transported, so that a barrier 34 is formed which serves to distribute the foam over the width and to prevent the admission of air into the space between the lining sheets 31 and 32.
  • the foam After passing under the roller 33, the foam begins to expand further owing to the chemical reaction which now starts (35).
  • Figure 4a shows an arrangement for the production of block foam as in Figure 4, but with an auxiliary lining sheet 50 being conveyed from above in the direction towards the lower lining sheet 31.
  • the auxiliary lining sheet 50 is drawn along the lower lining sheet 31 by means of a roller 51 and is led back and wound again round roller 52.
  • the liquid foam 30 is conveyed into the trough 54 formed by the essentially vertical upper lining sheet 32 and the auxiliary lining sheet 50.
  • Figure 5 shows an alternative embodiment of the expansion device 10 according to the invention in cross-section.
  • the expanding device is constructed in the form of two concentric tubular screens 21a and 21b.
  • the reaction mixture containing liquid carbon dioxide is fed along arrow 23.
  • the foam passes out over the entire circumference of the tubular screens.
  • the tubular screens 21a and 21b can be of diameters in the range of only a few centimeters.
  • Figure 6 shows a cross-section AA through the device as in Figure 5.
  • Figure 7 also shows a cross-section through the device as in Figure 5 but with a cover 25 being provided so as to ensure that the exit of the foam is directed only within a segment indicated by the arrows 24, while maintaining the mechanical stability of the symmetrical rotary screens 21a and 21b.
  • the cover unit 25 consists of a tube of the same length as the tubular screens, from which has been removed a paraxial segment of, for example, 90°. Since at least two screens in tandem are employed, the cover unit can be bonded between them or else mounted outside.
  • Figures 8 and 9 show a device 10 according to the invention consisting of a steel tube 26 closed on both sides, out of which a paraxial segment is drilled to receive the curved screen surfaces 21a and 21b.
  • the curved steel screens can, for example, be welded on (27).
  • the reaction mixture containing liquid carbon dioxide is fed along arrow 23 through the attached tube 18.
  • the foam leaves along arrows 24.
  • the width of the device can correspond to the width of the block foam to be produced.
  • Figure 10 shows the use according to the invention of the screen devices as in Figures 8 and 9 for the production of block foam.
  • the expansion device 10 is positioned between the deflection drums 40 and 41 which guide the lining sheets 31 and 32.
  • the lining sheets 31 and 32 are preferably guided so that they slide past the foam discharging device 10, so that the admission of air between the sheets 31 and 32 is prevented.
  • the sheets 31 and 32 have been shown at a distance from the foam-discharging device.
  • Figure 11 shows a device similar to that in Figure 8, but with the tube 26 being open at both sides and the reaction mixture being supplied through tubes 18 attached at both sides.
  • the advantage of this embodiment of the invention is apparent from Figure 12.
  • Figure 12 shows an arrangement similar to Figure 10, but with the upper lining sheet 32 being guided over the side of the tube 26 turned away from the screen, so that the supply tubes 18 encompass the lining sheet 32.
  • the deflection drums 40 and 41 can be arranged so that they are in contact with one another and thus form a space between the lining sheets 31 and 32 which is closed towards the rear.

Landscapes

  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Treatment Of Sludge (AREA)
  • Fertilizers (AREA)

Claims (7)

  1. Verfahren zur Herstellung von Schäumen aus wenigstens zwei reaktiven Komponenten unter Verwendung von Kohlendioxid als Treibmittel, umfassend das Vermischen wenigstens einer der reaktiven Komponenten mit Kohlendioxid unter Druck, wodurch eine Mischung hergestellt wird, die flüssiges Kohlendioxid enthält, das Vermischen der sich ergebenden Mischung mit der anderen reaktiven Komponente, um eine verschäumbare reaktive Mischung bei einem Druck zu bilden, der größer ist als der Gleichgewichtsdruck des gelösten Kohlendioxids, das Verschäumen der reaktiven Mischung und das Härten des sich ergebenden Schaumprodukts, dadurch gekennzeichnet, dass die verschäumbare reaktive Mischung geschäumt wird, indem man die reaktive Mischung durch Unterteilung in eine große Anzahl einzelner Ströme bei Schergeschwindigkeiten von größer als 500/s durch wenigstens ein feinmaschiges Sieb leitet.
  2. Verfahren gemäß Anspruch 1, wobei das Sieb eine Maschenweite von 0,025 bis 0,3 mm hat.
  3. Verfahren gemäß den Ansprüchen 1 oder 2, wobei jeder einzelne Strom eine Fließrate von 0,005 bis 0,2 ml/min aufweist.
  4. Vorrichtung zur Abgabe einer verschäumbaren, reaktiven Zweikomponentenmischung, die flüssiges Kohlendioxid enthält, aus einer Mischvorrichtung, wobei die reaktiven Komponenten in einem Werkzeug oder auf einem Förderband vermischt werden, dadurch gekennzeichnet, dass wenigstens zwei hintereinander angeordnete feinmaschige Siebe zwischen dem Werkzeug oder Förderband und der Mischvorrichtung vorliegen, und wobei die hintereinander angeordneten Siebe nicht mehr als 5 mm voneinander getrennt sind.
  5. Vorrichtung gemäß Anspruch 4, wobei zwei bis fünf hintereinander angeordnete Siebe zwischen dem Werkzeug oder Förderband und der Mischvorrichtung vorliegen.
  6. Vorrichtung gemäß den Ansprüchen 4 oder 5, wobei die Siebe eine Maschenweite von 0,025 bis 0,3 mm haben.
  7. Vorrichtung gemäß Anspruch 6, wobei die Maschenweite von 0,05 bis 0,15 mm reicht.
EP95924245A 1994-06-28 1995-06-16 Verfahren und vorrichtung zur schaumherstellung mittels unter druck gelöstem kohlendioxid Expired - Lifetime EP0767728B2 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4422568A DE4422568C1 (de) 1994-06-28 1994-06-28 Verfahren und Vorrichtung zur Schaumherstellung mittels unter Druck gelöstem Kohlendioxid
DE4422568 1994-06-28
PCT/EP1995/002322 WO1996000644A1 (en) 1994-06-28 1995-06-16 Method and device for the production of foam using carbon dioxide dissolved under pressure

Publications (3)

Publication Number Publication Date
EP0767728A1 EP0767728A1 (de) 1997-04-16
EP0767728B1 EP0767728B1 (de) 1998-05-20
EP0767728B2 true EP0767728B2 (de) 2003-04-16

Family

ID=6521688

Family Applications (1)

Application Number Title Priority Date Filing Date
EP95924245A Expired - Lifetime EP0767728B2 (de) 1994-06-28 1995-06-16 Verfahren und vorrichtung zur schaumherstellung mittels unter druck gelöstem kohlendioxid

Country Status (9)

Country Link
US (1) US5789457A (de)
EP (1) EP0767728B2 (de)
JP (1) JP3201415B2 (de)
CN (1) CN1066095C (de)
AU (1) AU2883395A (de)
DE (2) DE4422568C1 (de)
NO (1) NO309639B1 (de)
WO (1) WO1996000644A1 (de)
ZA (1) ZA955309B (de)

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FR2780409B1 (fr) 1998-06-30 2001-07-13 Omya Sa Procede pour traiter une charge minerale par un phosphate, charge minerale ainsi traitee, mousses de polyurethanne et polyurethannes composites utilisant cette charge, objets moules ou non les contenant
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ITMI20090028A1 (it) 2009-01-14 2010-07-15 Afros Spa Procedimento e dispositivo raffreddato per l'erogazione di miscele poliuretaniche.
US8794600B2 (en) * 2011-06-06 2014-08-05 Wu-Chiao Chou Bubble generating device
DE102013016661A1 (de) * 2013-10-09 2015-04-09 Hennecke Gmbh Verfahren zum kontinuierlichen Herstellen eines Stranges aus Reaktivkunststoff
EP3127678B1 (de) * 2015-08-07 2024-05-01 SMP Deutschland GmbH Vorrichtung und verfahren zur kunststoffbeschäumung
TWI758215B (zh) 2021-07-28 2022-03-11 國立清華大學 高鉻矽耐蝕鋼及其用途

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Also Published As

Publication number Publication date
JP3201415B2 (ja) 2001-08-20
WO1996000644A1 (en) 1996-01-11
US5789457A (en) 1998-08-04
DE69502608D1 (de) 1998-06-25
JPH10504771A (ja) 1998-05-12
DE4422568C1 (de) 1996-02-15
DE69502608T2 (de) 1998-09-10
CN1153494A (zh) 1997-07-02
EP0767728B1 (de) 1998-05-20
ZA955309B (en) 1996-02-12
NO965281D0 (no) 1996-12-10
EP0767728A1 (de) 1997-04-16
NO965281L (no) 1996-12-10
NO309639B1 (no) 2001-03-05
DE69502608T3 (de) 2003-12-11
AU2883395A (en) 1996-01-25
CN1066095C (zh) 2001-05-23

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